The demand for advanced energy storage drives an urgency to accelerate material discovery in solid-state electrolytes. In pursuit of this aim, this study presents an innovative methodology that integrates materials science insights with machine learning techniques to improve the ionic conductivity prediction in garnet-based solid electrolytes. Utilizing an expanded dataset comprising 362 data points, and exploiting easily obtainable pre-synthesis inputs, our approach incorporates rigorous data preprocessing inspired by materials science and machine learning methodologies. Through systematic feature selection and hyperparameter tuning, the model achieved an improved R-squared value of 0.85. This study highlights the efficacy of the proposed approach and underscores the potential of machine learning in streamlining materials discovery and design for next-generation solid-state batteries.
对先进储能技术的需求推动了加快固态电解质材料发现的紧迫性。为了实现这一目标，本研究提出了一种创新方法，将材料科学见解与机器学习技术相结合，以改进石榴石基固体电解质的离子电导率预测。利用由 362 个数据点组成的扩展数据集，并利用容易获得的合成前输入，我们的方法结合了受材料科学和机器学习方法启发的严格数据预处理。通过系统的特征选择和超参数调整，模型的 R 方值提高到了 0.85。这项研究凸显了所提方法的功效，并强调了机器学习在简化下一代固态电池的材料发现和设计方面的潜力。
{"title":"Data refinement for enhanced ionic conductivity prediction in garnet-type solid-state electrolytes","authors":"Zakaria Kharbouch , Mustapha Bouchaara , Fadila Elkouihen , Abderrahmane Habbal , Ahmed Ratnani , Abdessamad Faik","doi":"10.1016/j.ssi.2024.116713","DOIUrl":"10.1016/j.ssi.2024.116713","url":null,"abstract":"<div><div>The demand for advanced energy storage drives an urgency to accelerate material discovery in solid-state electrolytes. In pursuit of this aim, this study presents an innovative methodology that integrates materials science insights with machine learning techniques to improve the ionic conductivity prediction in garnet-based solid electrolytes. Utilizing an expanded dataset comprising 362 data points, and exploiting easily obtainable pre-synthesis inputs, our approach incorporates rigorous data preprocessing inspired by materials science and machine learning methodologies. Through systematic feature selection and hyperparameter tuning, the model achieved an improved R-squared value of 0.85. This study highlights the efficacy of the proposed approach and underscores the potential of machine learning in streamlining materials discovery and design for next-generation solid-state batteries.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116713"},"PeriodicalIF":3.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142423113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-10DOI: 10.1016/j.ssi.2024.116714
Asma Hajji, Ahmed Souemti, Adel Megriche
This study aimed to provide insight into how ultrasonic treatment affects microstructure, electrical properties, and physicochemical characteristics. Sonochemical ultrasound synthesis offers a distinct advantage over traditional methods by creating precise reaction conditions through acoustic cavitation. This process induces high temperatures and pressures in a liquid environment, facilitating the synthesis of materials with specific structures, sizes, and properties. In response to this capability, we developed low-cost M2P2O7 (M = Co, Mn) phosphate materials known as CoP and MnP. The samples were analysed for their crystalline structure, surface morphology, and elemental composition via X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).
The electrochemical performance of the samples was assessed via complex impedance spectroscopy methods. The results demonstrate that the samples exhibit excellent semiconductor behavior, indicating their potential for use in energy and catalytic applications.
{"title":"Ultrasound-assisted sonochemical synthesis of M2P2O7 (M = Co, Mn) nanomaterials: Enhanced structural morphology and ionic conduction mechanism","authors":"Asma Hajji, Ahmed Souemti, Adel Megriche","doi":"10.1016/j.ssi.2024.116714","DOIUrl":"10.1016/j.ssi.2024.116714","url":null,"abstract":"<div><div>This study aimed to provide insight into how ultrasonic treatment affects microstructure, electrical properties, and physicochemical characteristics. Sonochemical ultrasound synthesis offers a distinct advantage over traditional methods by creating precise reaction conditions through acoustic cavitation. This process induces high temperatures and pressures in a liquid environment, facilitating the synthesis of materials with specific structures, sizes, and properties. In response to this capability, we developed low-cost M<sub>2</sub>P<sub>2</sub>O<sub>7</sub> (M = Co, Mn) phosphate materials known as CoP and MnP. The samples were analysed for their crystalline structure, surface morphology, and elemental composition via X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).</div><div>The electrochemical performance of the samples was assessed via complex impedance spectroscopy methods. The results demonstrate that the samples exhibit excellent semiconductor behavior, indicating their potential for use in energy and catalytic applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116714"},"PeriodicalIF":3.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142423115","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-07DOI: 10.1016/j.ssi.2024.116703
Jiawang Ma, Yajie Wang, Tao Ban, Song Liu, Maolian Guo, Xinxin Wang, Zihui Wang, Xiuling Zhu
Proton exchange membrane (PEM) is an important component that affects the cost and cell performance of PEM water electrolysis (PEMWE). In this study, a series of ether-free poly(p-terphenyl-isatin- dimethylfluorene) (PID-x) polymers were synthesized by superacid-catalyzed Friedel-Crafts alkylation. The transparent PEMs of sulfonated poly(p-terphenyl-isatin- dimethylfluorene) (SPID-x) were prepared by the solution casting method. Introduction of dimethylfluorene groups enhances proton conductivity of PEMs while also preserving their high dimensional stability. The results indicate that the synthesized PID-x has excellent solubility in non-protic polar solvents. SPID-5, prepared with 5 % dimethylfluorene in the backbone structure exhibits a high conductivity of 0.176 S·cm−1 at 80 °C (compared to 0.155 S·cm−1 at 80 °C for Nafion115) and excellent dimensional stability, with a swelling ratio of only 10 % at 80 °C (compared to 20 % at 80 °C for Nafion115). In the water electrolysis cell performance test, SPID-25 achieved a current density of 167 mA·cm−2 at 2.5 V, outperforming the commercial Nafion 211 (151 mA·cm−2) at a similar membrane thickness.
{"title":"Efficient ether-free poly(p-terphenyl-isatin-dimethylfluorene) for proton exchange membrane water electrolysis","authors":"Jiawang Ma, Yajie Wang, Tao Ban, Song Liu, Maolian Guo, Xinxin Wang, Zihui Wang, Xiuling Zhu","doi":"10.1016/j.ssi.2024.116703","DOIUrl":"10.1016/j.ssi.2024.116703","url":null,"abstract":"<div><div>Proton exchange membrane (PEM) is an important component that affects the cost and cell performance of PEM water electrolysis (PEMWE). In this study, a series of ether-free poly(<em>p</em>-terphenyl-isatin- dimethylfluorene) (PID-x) polymers were synthesized by superacid-catalyzed Friedel-Crafts alkylation. The transparent PEMs of sulfonated poly(<em>p</em>-terphenyl-isatin- dimethylfluorene) (SPID-x) were prepared by the solution casting method. Introduction of dimethylfluorene groups enhances proton conductivity of PEMs while also preserving their high dimensional stability. The results indicate that the synthesized PID-x has excellent solubility in non-protic polar solvents. SPID-5, prepared with 5 % dimethylfluorene in the backbone structure exhibits a high conductivity of 0.176 S·cm<sup>−1</sup> at 80 °C (compared to 0.155 S·cm<sup>−1</sup> at 80 °C for Nafion115) and excellent dimensional stability, with a swelling ratio of only 10 % at 80 °C (compared to 20 % at 80 °C for Nafion115). In the water electrolysis cell performance test, SPID-25 achieved a current density of 167 mA·cm<sup>−2</sup> at 2.5 V, outperforming the commercial Nafion 211 (151 mA·cm<sup>−2</sup>) at a similar membrane thickness.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116703"},"PeriodicalIF":3.0,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142423116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-28DOI: 10.1016/j.ssi.2024.116708
Heng Pan, Lingcong Fan, Yongxi Zhang, Lei Zhang, Ying Shi, Jianjun Xie, Fang Lei
Garnet-type electrolytes are regarded as one of the most promising solid-state electrolytes (SSEs) for lithium-ion batteries due to their potential advantages in terms of energy density, electrochemical stability and safety. To achieve the maximum energy density, it is necessary to ensure that the electrolyte layer is as thin as possible. Nevertheless, thin sheet SSE is more challenging to sinter than pellet due to the greater lithium volatilization from the high surface/volume ratio. Garnet-type SSE (Li6.5La3Zr1.5Ta0.5O12, LLZTO) green tape was prepared by the tape-casting technique. The effects of supporter, sintering temperature and dwell time on the relative density, microstructure and ionic conductivity of thin sheet were investigated. A ceramic SSE sheet with a thickness of 173 μm, a relative density of 97.2 %, an ionic conductivity of 2.02 × 10−4 S/cm at 25 °C and an activation energy of 0.25 eV, was achieved using a rapid pressureless sintering at 1250 °C for 25 min with a MgO supporter. This work offers insights into the practical production of LLZTO sheets.
{"title":"A rapid pressureless sintering strategy for LLZTO ceramic solid electrolyte sheets prepared by tape casting","authors":"Heng Pan, Lingcong Fan, Yongxi Zhang, Lei Zhang, Ying Shi, Jianjun Xie, Fang Lei","doi":"10.1016/j.ssi.2024.116708","DOIUrl":"10.1016/j.ssi.2024.116708","url":null,"abstract":"<div><div>Garnet-type electrolytes are regarded as one of the most promising solid-state electrolytes (SSEs) for lithium-ion batteries due to their potential advantages in terms of energy density, electrochemical stability and safety. To achieve the maximum energy density, it is necessary to ensure that the electrolyte layer is as thin as possible. Nevertheless, thin sheet SSE is more challenging to sinter than pellet due to the greater lithium volatilization from the high surface/volume ratio. Garnet-type SSE (Li<sub>6.5</sub>La<sub>3</sub>Zr<sub>1.5</sub>Ta<sub>0.5</sub>O<sub>12</sub>, LLZTO) green tape was prepared by the tape-casting technique. The effects of supporter, sintering temperature and dwell time on the relative density, microstructure and ionic conductivity of thin sheet were investigated. A ceramic SSE sheet with a thickness of 173 μm, a relative density of 97.2 %, an ionic conductivity of 2.02 × 10<sup>−4</sup> S/cm at 25 °C and an activation energy of 0.25 eV, was achieved using a rapid pressureless sintering at 1250 °C for 25 min with a MgO supporter. This work offers insights into the practical production of LLZTO sheets.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116708"},"PeriodicalIF":3.0,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142357886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-28DOI: 10.1016/j.ssi.2024.116706
Sangtae Kim , Sergey Khodorov , Leonid Chernyak , Thomas Defferriere , Harry Tuller , Igor Lubomirsky
We propose a method for determining the density of space charge trapped at grain boundaries in polycrystalline solid state ionic conductors. The method is an extension of the earlier proposed Linear Diffusion Model (LDM) that relies on the impedance spectra-derived current-voltage characteristics of grain boundaries. The utility of the extended LDM version is demonstrated to successfully and nondestructively obtain values for the space charge density trapped at the grain boundaries in a variety of oxygen ion conductors including Sr-doped LaGaO3, Y-doped CeO2, and Gd-doped CeO2, and proton conductors including Sr-doped LaNbO3 and Y-doped BaZrO3. For all cases, the density of the space charge trapped at the grain boundaries was <0.2C/m2, corresponding to a fraction of electron charge per unit cell. The proposed technique, while it lacks the ability to determine the thickness of the grain boundary core when much smaller than the Debye length, it can be used to distinguish between space charge vs insulating layer contributions to the grain boundary resistance.
我们提出了一种确定多晶固态离子导体晶界空间电荷密度的方法。该方法是早先提出的线性扩散模型（LDM）的扩展，它依赖于从阻抗谱得到的晶界电流-电压特性。我们展示了扩展 LDM 版本的实用性，它成功地以无损方式获得了掺杂 Sr 的 LaGaO3、掺杂 Y 的 CeO2 和掺杂 Gd 的 CeO2 等多种氧离子导体以及掺杂 Sr 的 LaNbO3 和掺杂 Y 的 BaZrO3 等质子导体中晶界处捕获的空间电荷密度值。在所有情况下，晶界捕获的空间电荷密度均为 0.2C/m2，相当于每个单位晶胞的电子电荷分数。所提出的技术虽然无法确定远小于德拜长度的晶界核心厚度，但可以用来区分空间电荷和绝缘层对晶界电阻的贡献。
{"title":"Quantitative determination of charge trapped at grain boundaries in ionic conductors by impedance spectroscopy","authors":"Sangtae Kim , Sergey Khodorov , Leonid Chernyak , Thomas Defferriere , Harry Tuller , Igor Lubomirsky","doi":"10.1016/j.ssi.2024.116706","DOIUrl":"10.1016/j.ssi.2024.116706","url":null,"abstract":"<div><div>We propose a method for determining the density of space charge trapped at grain boundaries in polycrystalline solid state ionic conductors. The method is an extension of the earlier proposed Linear Diffusion Model (LDM) that relies on the impedance spectra-derived current-voltage characteristics of grain boundaries. The utility of the extended LDM version is demonstrated to successfully and nondestructively obtain values for the space charge density trapped at the grain boundaries in a variety of oxygen ion conductors including Sr-doped LaGaO<sub>3</sub>, Y-doped CeO<sub>2</sub>, and Gd-doped CeO<sub>2</sub>, and proton conductors including Sr-doped LaNbO<sub>3</sub> and Y-doped BaZrO<sub>3</sub>. For all cases, the density of the space charge trapped at the grain boundaries was <0.2C/m<sup>2</sup>, corresponding to a fraction of electron charge per unit cell. The proposed technique, while it lacks the ability to determine the thickness of the grain boundary core when much smaller than the Debye length, it can be used to distinguish between space charge vs insulating layer contributions to the grain boundary resistance.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116706"},"PeriodicalIF":3.0,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142357885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-27DOI: 10.1016/j.ssi.2024.116707
Vimi Dua, K. Singh
Composition of 75V2O5-(25-x) MgO-(x) K2O (x = 6, 9, 12, and 15 mol%) are synthesized by melt quench technique. All the as quenched samples either formed the glasses or glass ceramic as confirmed by differential scanning calorimeter (DSC) and X-ray diffraction (XRD). The DSC curves exhibited the two glass transition temperatures (Tg), two crystallization temperatures (Tc), and with two melting temperatures (Tm) which could be related to the presence of two distinct glass in the present samples. The K2O content increases the devitrification tendency of as quenched samples and formed the crystalline phases i.e. K3VO4 along with glassy phase in higher concentration of K2O. X-ray photoelectron spectroscopy (XPS) is confirmed that the vanadium exhibit two oxidation states V4+ / V5+. The highest ratio of V4+/V5+ is found in (x = 15) sample which exhibited the highest conductivity i.e. 1.3 × 10−3 S/cm at 250 °C. It is two orders higher than the (x = 6) sample at 250 °C. The high conducting glass ceramics can be used as cathode in all solid state battery and fuel cells.
{"title":"Enhancement in conductivity by K2O in MgO-V2O5 glass-ceramic for solid- state battery application","authors":"Vimi Dua, K. Singh","doi":"10.1016/j.ssi.2024.116707","DOIUrl":"10.1016/j.ssi.2024.116707","url":null,"abstract":"<div><div>Composition of 75V<sub>2</sub>O<sub>5</sub>-(25-x) MgO-(x) K<sub>2</sub>O (x = 6, 9, 12, and 15 mol%) are synthesized by melt quench technique. All the as quenched samples either formed the glasses or glass ceramic as confirmed by differential scanning calorimeter (DSC) and X-ray diffraction (XRD). The DSC curves exhibited the two glass transition temperatures (T<sub>g</sub>), two crystallization temperatures (T<sub>c</sub>)<sub>,</sub> and with two melting temperatures (T<sub>m</sub>) which could be related to the presence of two distinct glass in the present samples. The K<sub>2</sub>O content increases the devitrification tendency of as quenched samples and formed the crystalline phases i.e. K<sub>3</sub>VO<sub>4</sub> along with glassy phase in higher concentration of K<sub>2</sub>O. X-ray photoelectron spectroscopy (XPS) is confirmed that the vanadium exhibit two oxidation states V<sup>4+</sup> / V<sup>5+</sup>. The highest ratio of V<sup>4+</sup>/V<sup>5+</sup> is found in (x = 15) sample which exhibited the highest conductivity i.e. 1.3 × 10<sup>−3</sup> S/cm at 250 °C. It is two orders higher than the (x = 6) sample at 250 °C. The high conducting glass ceramics can be used as cathode in all solid state battery and fuel cells.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116707"},"PeriodicalIF":3.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-25DOI: 10.1016/j.ssi.2024.116705
Patrick Pretschuh, Andreas Egger, Edith Bucher
High-entropy perovskites (HEPs) are attracting increasing attention as air electrode materials for solid oxide cells (SOCs). In this work, three different HEPs from the series La0.2Pr0.2Nd0.2Sm0.2Sr0.2Co1-xFexO3-δ (x = 0, 0.5, 1) are synthesized using the citric acid-ethylenediaminetetraacetate (EDTA) method. X-ray diffraction analysis finds crystal structures with the orthorhombic space group 62 (Pnma) at room temperature. The lattice distortion increases with increased Fe-substitution at the B-site. The electrical conductivity (σe) is determined at temperatures from 600 to 850 °C and oxygen partial pressures (pO2) between 0.001 and 0.15 bar. For the pure cobaltate, σe is 1469 S cm−1 at 800 °C and 0.15 bar pO2. The conductivity is significantly reduced with Fe-doping, reaching 87 S cm−1 for the pure ferrate at 800 °C. The chemical oxygen surface exchange coefficient (kchem) and the chemical oxygen diffusion coefficient (Dchem) are determined by the electrical conductivity relaxation technique. Dchem is found to be quite independent of B-site doping and pO2, with values of approx. 5 × 10−6 cm2 s−1 at 800 °C. In contrast, kchem is strongly influenced by the B-site composition, which results in an increase of more than one order of magnitude from the ferrate (3.4 × 10−5 cm s−1) to the cobaltate (7.7 × 10−4 cm s−1) at 800 °C and 0.001 bar pO2. This clearly demonstrates the beneficial effects of Co on the electronic conductivity as well as on the catalytic activity for the oxygen surface exchange reaction.
作为固体氧化物电池（SOC）的空气电极材料，高熵过氧化物（HEPs）正受到越来越多的关注。在这项工作中，采用柠檬酸-乙二胺四乙酸盐（EDTA）法合成了 La0.2Pr0.2Nd0.2Sm0.2Sr0.2Co1-xFexO3-δ （x = 0、0.5、1）系列的三种不同的 HEP。X 射线衍射分析发现，该化合物在室温下具有正交空间群 62（Pnma）的晶体结构。晶格畸变随着 B 位上 Fe 取代度的增加而增大。电导率（σe）是在温度为 600 至 850 ℃、氧分压（pO2）为 0.001 至 0.15 巴的条件下测定的。对于纯钴酸盐，在 800 °C 和 0.15 巴 pO2 条件下，σe 为 1469 S cm-1。掺入铁元素后，电导率明显降低，纯铁在 800 ℃ 时的电导率为 87 S cm-1。化学氧表面交换系数（kchem）和化学氧扩散系数（Dchem）是通过电导弛豫技术测定的。发现 Dchem 与 B 位掺杂和 pO2 完全无关，在 800 ℃ 时的值约为 5 × 10-6 cm2 s-1。相比之下，Kchem 受 B 位成分的影响很大，在 800 °C 和 0.001 巴 pO2 条件下，从铁酸盐（3.4 × 10-5 cm s-1）到钴酸盐（7.7 × 10-4 cm s-1），Kchem 增加了一个数量级以上。这清楚地表明了钴对电子导电性以及氧表面交换反应催化活性的有利影响。
{"title":"Crystal structure, electronic conductivity and oxygen exchange kinetics of high-entropy perovskites La0.2Pr0.2Nd0.2Sm0.2Sr0.2Co1-xFexO3-δ (x = 0, 0.5, 1)","authors":"Patrick Pretschuh, Andreas Egger, Edith Bucher","doi":"10.1016/j.ssi.2024.116705","DOIUrl":"10.1016/j.ssi.2024.116705","url":null,"abstract":"<div><div>High-entropy perovskites (HEPs) are attracting increasing attention as air electrode materials for solid oxide cells (SOCs). In this work, three different HEPs from the series La<sub>0.2</sub>Pr<sub>0.2</sub>Nd<sub>0.2</sub>Sm<sub>0.2</sub>Sr<sub>0.2</sub>Co<sub>1-x</sub>Fe<sub>x</sub>O<sub>3-δ</sub> (x = 0, 0.5, 1) are synthesized using the citric acid-ethylenediaminetetraacetate (EDTA) method. X-ray diffraction analysis finds crystal structures with the orthorhombic space group 62 (<em>Pnma</em>) at room temperature. The lattice distortion increases with increased Fe-substitution at the B-site. The electrical conductivity (<em>σ</em><sub>e</sub>) is determined at temperatures from 600 to 850 °C and oxygen partial pressures (<em>p</em>O<sub>2</sub>) between 0.001 and 0.15 bar. For the pure cobaltate, <em>σ</em><sub>e</sub> is 1469 S cm<sup>−1</sup> at 800 °C and 0.15 bar <em>p</em>O<sub>2</sub>. The conductivity is significantly reduced with Fe-doping, reaching 87 S cm<sup>−1</sup> for the pure ferrate at 800 °C. The chemical oxygen surface exchange coefficient (<em>k</em><sub>chem</sub>) and the chemical oxygen diffusion coefficient (<em>D</em><sub>chem</sub>) are determined by the electrical conductivity relaxation technique. <em>D</em><sub>chem</sub> is found to be quite independent of B-site doping and <em>p</em>O<sub>2</sub>, with values of approx. 5 × 10<sup>−6</sup> cm<sup>2</sup> s<sup>−1</sup> at 800 °C. In contrast, <em>k</em><sub>chem</sub> is strongly influenced by the B-site composition, which results in an increase of more than one order of magnitude from the ferrate (3.4 × 10<sup>−5</sup> cm s<sup>−1</sup>) to the cobaltate (7.7 × 10<sup>−4</sup> cm s<sup>−1</sup>) at 800 °C and 0.001 bar <em>p</em>O<sub>2</sub>. This clearly demonstrates the beneficial effects of Co on the electronic conductivity as well as on the catalytic activity for the oxygen surface exchange reaction.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116705"},"PeriodicalIF":3.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319467","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-20DOI: 10.1016/j.ssi.2024.116701
Koki Kitabayashi , Junji Hyodo , Nai Shi , Yoshihiro Yamazaki
Liquid ammonia is an attractive candidate for use as a hydrogen carrier because of its high volumetric density. The successful development of direct ammonia proton-conducting ceramic fuel cells (PCFCs) operating at intermediate temperatures can be seamlessly integrated into the current infrastructure without the need for investing in hydrogen gas pipelines and storage facilities. However, the low power output of PCFCs using ammonia fuel hinders their practical applications. In this study, we systematically investigated the ammonia conversion ratio and rate, maximum power density, open-circuit voltage, and ohmic and polarization resistances of PCFCs (Ni-BaCe0.7Zr0.1Y0.1Yb0.1O3−δ |BaCe0.7Zr0.1Y0.1Yb0.1O3−δ| PrBaCo2O5+δ) for ammonia and hydrogen fuels at intermediate temperatures of 500–650 °C and quantitatively assessed the impact of Ru catalyst loading on the electrochemical performance of direct ammonia PCFC. Ru loading improved the maximum power density of the direct ammonia PCFC from 100 to 149 mWcm−2 at 500 °C. Combined analysis of gas chromatography and AC impedance spectroscopy revealed that Ru catalysts improved the internal ammonia reforming rate by a factor of 1.9 at 500 °C and reduced polarization resistance by a factor of 1.4 at 500 °C. All results consistently support that the enhanced maximum power density of the direct ammonia PCFC is predominantly attributed to the improved electrochemical reaction kinetics at the electrode/electrolyte/gas interface.
{"title":"Quantitative assessment of enhanced performance of Ru-loaded direct ammonia proton ceramic fuel cells","authors":"Koki Kitabayashi , Junji Hyodo , Nai Shi , Yoshihiro Yamazaki","doi":"10.1016/j.ssi.2024.116701","DOIUrl":"10.1016/j.ssi.2024.116701","url":null,"abstract":"<div><p>Liquid ammonia is an attractive candidate for use as a hydrogen carrier because of its high volumetric density. The successful development of direct ammonia proton-conducting ceramic fuel cells (PCFCs) operating at intermediate temperatures can be seamlessly integrated into the current infrastructure without the need for investing in hydrogen gas pipelines and storage facilities. However, the low power output of PCFCs using ammonia fuel hinders their practical applications. In this study, we systematically investigated the ammonia conversion ratio and rate, maximum power density, open-circuit voltage, and ohmic and polarization resistances of PCFCs (Ni-BaCe<sub>0.7</sub>Zr<sub>0.1</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3−δ</sub> |BaCe<sub>0.7</sub>Zr<sub>0.1</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3−δ</sub>| PrBaCo<sub>2</sub>O<sub>5+δ</sub>) for ammonia and hydrogen fuels at intermediate temperatures of 500–650 °C and quantitatively assessed the impact of Ru catalyst loading on the electrochemical performance of direct ammonia PCFC. Ru loading improved the maximum power density of the direct ammonia PCFC from 100 to 149 mWcm<sup>−2</sup> at 500 °C. Combined analysis of gas chromatography and AC impedance spectroscopy revealed that Ru catalysts improved the internal ammonia reforming rate by a factor of 1.9 at 500 °C and reduced polarization resistance by a factor of 1.4 at 500 °C. All results consistently support that the enhanced maximum power density of the direct ammonia PCFC is predominantly attributed to the improved electrochemical reaction kinetics at the electrode/electrolyte/gas interface.</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116701"},"PeriodicalIF":3.0,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
BaZr0.1Ce0.7Y0.1Yb0.1O3-δ is a widely studied proton conductor for solid oxide fuel cells but its structure has not been examined in detail. In this study, we synthesized a pure, well-crystallized BaZr0.1Ce0.7Y0.1Yb0.1O3-δ powder via a glycine-nitrate process. Using Rietveld analysis on X-ray and neutron diffraction powder patterns collected both at room temperature and at elevated temperatures, we investigate the crystal structure of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ. At room temperature, the sample exhibits I4/mcm tetragonal symmetry, with cell parameters of a = 6.14911(7) Å and c = 8.87903(14) Å. The structure of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ can be described by a distortion of the ideal cubic perovskite (ap), resulting from the cooperative tilt of the (Zr,Ce,Y,Yb)O6 octahedra along the [001]p axis (tilt system a0a0c−). Within the octahedra, it consists of a disordered arrangement of Zr, Ce, Y, and Yb atoms with an average distance (Zr,Ce,Y,Yb)-O of 2.219 Å. At around 650 °C, BaZr0.1Ce0.7Y0.1Yb0.1O3-δ undergoes a phase transition to the primitive cubic structure Pmm. This transition is characterized by a progressive decrease in the tilt angle, indicating a continuous phase transition, and is tricritical in nature.
Crystallographic data for BaZr0.1Ce0.7Y0.1Yb0.1O3-δ obtained from neutron data have been deposited at the Cambridge Crystallographic Data Centre, CSD 2341244 (room temperature) and CSD 2341246–2341252 (100 to 700 °C).
BaZr0.1Ce0.7Y0.1Yb0.1O3-δ 是一种被广泛研究的用于固体氧化物燃料电池的质子导体，但其结构尚未得到详细研究。在这项研究中，我们通过硝酸甘油工艺合成了纯净、结晶良好的 BaZr0.1Ce0.7Y0.1Yb0.1O3-δ 粉末。通过对室温和高温下收集到的 X 射线和中子衍射粉末图进行里特维尔德分析，我们研究了 BaZr0.1Ce0.7Y0.1Yb0.1O3-δ 的晶体结构。在室温下，样品呈 I4/mcm 四边形对称，晶胞参数为 a = 6.14911(7) Å 和 c = 8.87903(14) Å。1O3-δ的结构可以用理想立方包晶（ap）的变形来描述，这是由于(Zr,Ce,Y,Yb)O6八面体沿[001]p轴协同倾斜（倾斜系统 a0a0c-）造成的。在八面体内部，它由 Zr、Ce、Y 和 Yb 原子的无序排列组成，(Zr,Ce,Y,Yb)-O 的平均距离为 2.219 Å。在 650 °C 左右，BaZr0.1Ce0.7Y0.1Yb0.1O3-δ 发生相变，变成原始立方结构 Pm3¯m。从中子数据中获得的 BaZr0.1Ce0.7Y0.1Yb0.1O3-δ 的晶体学数据已存放在剑桥晶体学数据中心，CSD 2341244（室温）和 CSD 2341246-2341252（100 至 700 °C）。
{"title":"Synthesis and temperature dependence of the crystal structure of proton conductor BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb1711) by combined neutron and X-ray diffraction","authors":"Lozane Hamze , Emmanuelle Suard , Olivier Joubert , Eric Quarez","doi":"10.1016/j.ssi.2024.116682","DOIUrl":"10.1016/j.ssi.2024.116682","url":null,"abstract":"<div><p>BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3-δ</sub> is a widely studied proton conductor for solid oxide fuel cells but its structure has not been examined in detail. In this study, we synthesized a pure, well-crystallized BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3-δ</sub> powder via a glycine-nitrate process. Using Rietveld analysis on X-ray and neutron diffraction powder patterns collected both at room temperature and at elevated temperatures, we investigate the crystal structure of BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3-δ</sub>. At room temperature, the sample exhibits <em>I</em>4<em>/mcm</em> tetragonal symmetry, with cell parameters of a = 6.14911(7) Å and c = 8.87903(14) Å. The structure of BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3-δ</sub> can be described by a distortion of the ideal cubic perovskite (<em>a</em><sub><em>p</em></sub>), resulting from the cooperative tilt of the (Zr,Ce,Y,Yb)O<sub>6</sub> octahedra along the [001]<sub>p</sub> axis (tilt system <em>a</em><sup>0</sup><em>a</em><sup>0</sup>c<sup>−</sup>). Within the octahedra, it consists of a disordered arrangement of Zr, Ce, Y, and Yb atoms with an average distance (Zr,Ce,Y,Yb)-O of 2.219 Å. At around 650 °C, BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3-δ</sub> undergoes a phase transition to the primitive cubic structure <em>Pm</em><span><math><mover><mn>3</mn><mo>¯</mo></mover></math></span><em>m</em>. This transition is characterized by a progressive decrease in the tilt angle, indicating a continuous phase transition, and is tricritical in nature.</p><p>Crystallographic data for BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3-δ</sub> obtained from neutron data have been deposited at the Cambridge Crystallographic Data Centre, CSD 2341244 (room temperature) and CSD 2341246–2341252 (100 to 700 °C).</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116682"},"PeriodicalIF":3.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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